Phenyl-azo-naphthol dyes

ABSTRACT

THE INVENTION RELATES TO MONOAZO DYESTUFFS WHICH, IN THE FORM OF THE FREE ACID, CORRESPOND TO THE FORMULA   2-((2-(HO3S-),(X-NH-)PHENYL)-N=N-),3-(HO3S-),5,6-DI(Y-),   8-(Z-NH-)NAPHTH-1-OL   IN WHICH ONE OF THE SYMBOLS Y RESPRESENTS A HYDROGEN ATOM AND THE OTHER SYMBOL Y REPRESENTS A SULPHONIC ACID GROUP Z REPESENTS AN ACYL GROUPING AND X REPRESENTS AN A-BROMACRYLIC GROUPING, AN AB,-DIBROMOPROPIONYL GROUPING, A MONO- OR DINITROCHLOROHBENZOYL OR A MONO- OR DINITROBENZENESULPHONYL GROUPING.

United States Patent US. Cl. 260-199 12 Claims ABSTRACT OF THEDISCLOSURE The invention relates to monoazo dyestuffs which, in the formof the free acid, correspond to the formula in which one of the symbolsY represents a hydrogen atom and the other symbol Y represents asulphonic acid group, Z represents an acyl grouping and X represents anoc-bIOIIlacrylic grouping, an a,;3-dibromopropionyl grouping, a monoordinitrochlorobenzoyl or a monoor dinitrobenzenesulphonyl grouping.

X-HN

The present invention provides valuable monoazo dyestulfs of the generalformula HOaS in which one of the symbols Y represents a hydrogen atomand the other symbol Y represents a sulphonic acid group, X represents amonoor dinitrochlorobenzoyl group or preferably an a-bromacrylic group(that is to say, a

group) or an a,B-dibromopropionyl group and Z represents an acylgrouping. The acyl substituent Z may be derived from a sulphonic acid orpreferably from a carboxylic acid. It is advantageously an a-bromacrylicresidue, an a,,5-dibromopropionyl residue or anB-bromacrylicaminobenzoyl or a,,8-dibromopropionylaminobenzoyl residue.

The dyestuff may be further described in the form of its free acid bythe following formula in which one of the symbols Y represents ahydrogen atom and the other symbol Y represents a sulphonic acid group,Z represents alkyl or alkenyl containing up to 4 carbon atoms, phenyl,alkylcarboxamidophenyl, alkenylcarboxamidophenyl containing up to 4carbon atoms in said alkyl and alkenyl chain, andphenylcarboxamidophenyl; and X represents an a-bromoacrylic grouping, an

u,B-dibromopropionyl grouping, a monoor di-nitrochlorobenzoyl grouping.

The dyestuffs may be manufactured by acylation, by coupling or, when thesubstituent represented by X is an a-bromacrylic group, by eliminationof hydrogen bromide. For example, diazo compounds derived from aromaticamines of the formula X-HN may be coupled with coupling components ofthe formula (3) H0 NHZ or of the formula no NHCO Hols-war in whichformulae the various symbols have the meanings ascribed to them inFormula 1. This also applies to all formulae hereinafter shown.

The coupling components of the Formula 3 used as starting materials inthe process may be prepared by 'known methods, for example, bymonoacylation of 1- amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonicacid with anhydrides or halides of sulphonic or carboxylic acids, foreirample, acetic, propionic, butyric or benzoic acid, and also with acidhalides containing fibre-reactive acyl residues. Those in which thesymbol Z represents an oc-bromacrylic grouping may also be prepared from04,,8- dibromopropionylamino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid by elimination of hydrogen bromide.

The following are given as examples of coupling components of theFormula 3:

1-acetylamino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-propiony1amino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-butyrylamino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-benzoylamino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-chloroacetylamino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-acrylamino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

1-(a,,8-dichloroor -dibromopropionylamino)-8-hydroxynaphthalene-3,6- or-4,6-disulphonic acid,

1- a-bromoacrylamino 8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid,

1-chlorobenzoylan1ino-8-hydroxynaphthalene-3,6- or -4,6-

disulphonic acid,

and also 1-(a,,B-dibromopropionylaminobenzoylamino)-8-hydroXynaphthalene-3,6- or -4,6-disulphonic acid.

3 The following are given as examples of diazo components that are to becoupled with the aforementioned coupling components:

HOaS

which are obtained by known methods, with halides of monoordinitrochlorobenzoic acid or wbromacrylic acid, for example, in anaqueous medium in the presence of an agent capable of binding acid. Thedyestuffs of the Formula l in which X and Z each represents an identicalacylamino group may also be manufactured by diacylating dyestuffs of theformula NHH which may be obtained by known methods, for example, in anaquaous medium, in the presence of an agent capable of binding acid.Furthermore, the u-bromacrylic derivative of the Formula 1 may also beobtained by the elimination of hydrogen bromide from the correspondinga,fl-dibromopropionyl compounds. Elimination of the hydrogen bromide iseffected by a known method, for example, by a treatment with an alkali.

The dyestuffs of the Formula 1 obtained by the process of the inventionand the modifications thereof are new. They are suitable for dyeing andprinting a very wide variety of materials, for example, materials ofanimal origin, for example, leather, silk and especially wool, and alsovarious man-made fibres, for example, polyamide and polyurethane fibres.They are specially suitable for application in a neutral to acid medium.The dyeings so obtained on wool exhibit excellent fastness to light,milling, perspiration and washing.

The new dyestuffs are also suitable for dyeing and printing cellulosicmaterials, for example, cotton and regenerated cellulose fibres,fixation being effected by a heat treatment in the presence of analkali, for example, in the presence of sodium carbonate, sodiumhydroxide or trisodium phosphate. Compared with known dyestuffs mostclosely comparable with those of the present invention, the dyestuffsobtained by the process of the invention display a higher degree ofsolubility, better properties of wet fastness and, in particular, betterbehaviour in the presence of levelling agents, especially in thepresence of polyglycol ether derivatives containing, on average, atleast 1OCH CH -O-- groups and which are de- 4 rived from primarymonoamines containing an aliphatic hydrocarbon residue having at least20 carbon atoms.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

EXAMPLE 1 40.2 parts of4-(a,B-dibromopropionylamino)-1-aminobenzene-2-sulphonic acid aredissolved in 600 parts of water in the presence of sodium carbonate; 30parts of 30% hydrochloric acid are added at 0 to 5 C. and diazotizationis effected with 25 parts by volume of 4 N sodium nitrite solution. Thediazo suspension, which is acid to Congo paper, is then added to asolution of 42.3 parts of 1-benzoylamino-8-hydroxynaphthalene 3,6disulphonic acid and 40 parts of sodium acetate in 400 parts of water.After coupling, the pH of the dyestuff is adjusted to 12 by the additionof 10 N sodium hydroxide solution, the temperature being kept at between10 and 15 C. by the addition of ice. After about 15 minutes, the batchis neutralized to pH 7 by the addition of hydrochloric acid, thedyestuff is precipitated by the addition of sodium chloride, isolated byfiltation and then dried in vacuo at to C.

The dyestuff so obtained which, in the form of the free acid,corresponds to the formula dyes wool fast, red-violet shades.

A dyestuff which dyes wool fast, bluish red shades may be obtained byreplacing the 4-(a,a-dibromopropionylamino)-1-aminobenzene-2-sulphonicacid with 5-(m,p-dibromopropionylamino)-1-aminobenzene-Z-sulphonic acid.

EXAMPLE 2 32-1 parts of 4-(a-bromacrylamino)-1-aminobenzene- 2-sulphonicacid are dissolved in 600 parts of water in the presence of sodiumcarbonate; 30 parts of 30% hydrochloric acid are added at O to 5 C. anddiazotization is effected with 25 parts by volume of 4 N sodium nitritesolution. The diazo suspension, which is acid to Congo paper, is addedto a solution of 42.3 parts ofl-benzoylamino-8-hydroxynaphthalene-3,6-disulphonic acid and 40 parts ofsodium acetate in 400 parts of water. After coupling, the dyestuff isprecipitated by the addition of sodium chloride, isolated by filtrationand then dried in vacuo at 70 to 80 C. The dyestuff so obtained isidentical with the dyestuff described in the first paragraph of example1.

A dyestuff which is identical with the dyestuff described in the secondparagraph of example 1 may be obtained by replacing the4-(u-bromacrylamino)-1-aminobenzene-2- sulphonic acid with5-(a-bromacrylamino)-1-arninobenzene-Z-sulphonic acid.

Dyestuffs which dye wool the shades indicated in Column III of thefollowing table may be obtained from the diazo components listed inColumn I by coupling with the coupling components listed in Column II inaccordance with the process described in Example 1.

The oaB-dibromopropionyl derivatives shown in C01- umns I and II may bereplaced by the corresponding a-bromacrylic derivatives, in which casethe procedure, described in Example 2 should be followed.

I II III 4-(a,fl-dibromopropionylamino)-1-ami11obenzene-2sulphonic acidl-acetylamino-Shydroxynaphthalene-3,6-disulphonic acid Rod. Dl-acetylamiuo-S-hydroxynaphthale11e4,6-disulphonic acid. Red.

. .-do propionylamiuo-R-laydroxynaphthalenc-LG-diwlphouiel-u-butyrylnrmno-R-hyrlroxynaphthalencA.fi-disulphonic acl-bcnzOylammo-S-hydroxyuaphthalone-4.6-disul phonic acid l-aeetylamiuo 8hydroxynaphthalcuc-3,6-disulphonic acid. Rtd.

i. l-chloroacetylamiuo-8-l1ydroxynaphthalcue-3.6- iisulphonic acid Red.

l-ehloioacetylammo-S-hydroxynaphthalone-4,6-di ulphonic acid d. Red.

l-acry1aminn-8-hydroxynaphthaleueAfi-disulphonic acid Red.

. -aclylau1in0-8-hydtnxyuaphthaleuc-Bfi-disulphonic acid Red.

...... 1-(a g-dibromopropl0nylamiuo-s-hydroxynaphthaleue3,ddisulphonieRed.

aci

Do 1-(a,t-dibromopropiouylamino-8-hydroxynaphthaIcncAfi-disulphonic Red.

acl

4-(a,fl-dibromopropionylamino)j1-amlnohenzene2-sulphonic acid"1-(a,%dibromopropiouylamino-8-hydroxynaphthalone-3,6-disulphonic Red.

aci

Do 1-(ocgdibromopropionylamino-8-hydroxynaphthalene-gfi disulphonic Red.

Do 1-bromoaCetylamino-8-hydroxyuaphtha1ene-4,fi-disulphonic acid Red.

EXAMPLE 3 simultaneous dropwise addition of an aqueous sodium 416 partsof (325, dinitr0 4, chlorobenzoylamino) 2O garbonate solution. After thetwo amino groups have 1-amino-benzene-Z-sulphonic acid are dissolved in.500 .Completely f i the dyestufi Completely parts of water in thepresence of sodium carbonate; 30% prfeclpltated by the addmon sodmmchlonde and than hydrochloric acid is added at 0 to 5 c. anddiazotization r vacuo at The dyestuff dyes is eifected with parts byvolume of 4 N sodium nitrite bhnsh red shades solution. The diazosuspension is added to a solution of 25 EXAMPLE .5 42.3 parts of1-benzoylamino-8-hydroxynaphthalene-3,6- disulphonic acid in 400 partsof water and 40 parts of sodium acetate. After coupling, the dyestuff iscompletely precipitated by the addition of sodium chloride, isolated byfiltration and then dried in vacuo at 80 to 90 C. The Zation is effectedwith 25 parts by volume of 4 N sodium dyestuff so obtamed dyes Wool fastbluish red shades nitrite solution. The diazo suspension is then addedto a Similar dyestuffs which also dye wool fast red shades solution of652 parts of 1[3%mfidibmmopmprionyb 40.2 parts of4-(a,/8-dibromopropionylamino)-1-aminobenzene-Z-sulphonic acid aredissolved in 600 parts of water in the presence of sodium carbonate; 30parts of 30% hydrochloric acid are added at 0 to 5 C. and diazotim y beObtained y ep s Y Q' Y' amino)-benzoylamino]-8-hydroxynaphthalene4,6-disuldroxypaththalenea6'd1su1Phmf: acld W1 th an eqmvalent phonicacid and 70 parts of sodium acetate crystals in proportion of one of thefollowing coupllng components: 600 parts of Waten After coupling, the PHof the dyestufi l-acetylamino-8-hydroxynaphthalene-3,6-disulphonic acid,is adjusted to 12 With a 10 N Sodium hydroxide Solution,l-acetylamino-8-hydroxynaphthalene 4,6 disulphonic the temperature beingp at between and acid, by the addition of ice. After 15 minutes, thebatch is neu- 1 propionylamino 8 hydroxynaphthalene 4,6 ditralized to pH7.0 with hydrochloric acid, the dyestuif sulphonic acid, is completelyprecipitated by the addition of sodium 1 n butyrylamino 3hydroxynaphthalene 4 6 dichloride, isolated by filtration and then driedat 70 to sulphonic acid, 80 C. in vacuo. The dyestuff so obtained which,in the 1 bemoylamino 8 hydroxynaphthalene 4 6 disula form of the freeacid, corresponds to the formula phonic acid, 1 chloroacetylamino 8hydroxynaphthalene 3,6 di- SIOBH R sulphonic acid, 1methanesulphonylamino 8 hydroxynaphthalene -3, Br 6-disulphonic acid, 1chloroacetylamino 8 hydroxynaphthalene 4,6 di HN Hms- NI'ICOC=CH2sulphonic acid, 1 acrylamino 8 hydroxynaphthalene-4,6 disulphonic 501Eacid, Br 1 :gylammo 8 hydroxynaphthalene 3,6 disulphonic dyes W001 fast,bluish red Shades. 1 (eat? dibromopropionylamino) 8 hydroxynaphtha-EXAMPLE 6 lene 4,6 disulphonic acid, 1 (i/3 dibromqpmpmqylammo) 8hydroxynaph' 32.1 parts of 4-(a-bromacrylamino)-l-aminobenzenethalenedlsulphomc acld and 2-sulphonic acid are dissolved in 600 parts of waterin 1 bromozilcetylammo 8 hydroxynaphthalene 4,6 6 the presence of sodiumcarbonate; 30 parts of 30% hydrosulphomc acldchloric acid are added at 0to 5 C. and diazotization is EXAMPLE 4 eifected with 25 parts by volumeof 4 N sodium nitrate solution. The diazo suspension is then added to asolution parts of dyestufi of the formula of 57.1 parts ofl-[3(u-bromacylamino)-benzoylarnino]-8-hydroxynaphthalene-4,6-disulphonic acid and parts of sodium acetatecrystals in 600 parts of water. After coupling, the dyestuff iscompletely precipitated by the addition of sodium chloride, isolated byfiltration and then Hots HO3S- SOiH dried in vacuo at 60 to 70 C. Thedyestuif so obtained is identical with the dyestutf described inExample 1. are neutralized in 300 parts of water with sodium car-Dyestuffs which dye wool the shades indicated in C01- bonate. A solutionof 6 parts of 3,5-dinitro-4-chlorobenumn III of the following table maybe obtained from the zoyl chloride in 30 parts of acetone is addeddropwise at diazo components listed in Column I by coupling with theroom temperature to the solution of the dyestulf, the pH couplingcomponents listed in Column II in accordance of the solution being keptat between 7 and 8 by the with the process described in Example 1.

7 The u,[3-dibromopropionyl derivatives shown in Columns I and Il may bereplaced by the corresponding a.- bromacrylic derivatives, in which casethe procedure described in Example 2 should be followed.

and alkenyl chain, and phenylcarboxamidophenyl; and X represents ana-bromoacrylic grouping, an a,B-dibromopropionyl grouping, a monoordi-nitrochlorobenzoyl grouping.

I II III 4-(a,B-dibromopropionylamino) 1-aminobenzene-Q-sulphonic acid.1-[4-(a,B-dibr0mopropionylamino)-benzoy1amino]-8-hydroxynaph-Red-violet.

thalene-3,6-disulphonic acid. D1-[4-(a,B-dibromopropionylamino)-benzoylamino]-8-hydroxynaph- Bluishred.

thalene-4,6-disu1phonic acid.5-(a,l3-dibromopropionylamino)-1-aminobenzene-Z-sulphonlc acid.]-[4-(a.B-dibromopropionylamino)-benz0ylarnin0]-8-hydroxynaph- Red.

tl1alene-3,6-disulph0nic acid. Do1-[4-(afi-dibromopropionylamino)benzoylamino]-8-hydroxynaph- Red.

thalene-3 ,6-disulphonic acid.1-[3-(a,fi-d1brom0propionylamino)-benzoylamino]-8-hydr0xynaph- Red.

thalene-? .6-disulphonio acid. Do1-[3-(a,B-dibromopropionylamino)-benzoylamino]-8-hydroxynaph- Red.

tlialane-4,6-disulphonic acid.

EXAMPLE 7 30 parts of 30% hydrochloric acid are added to 41.6 parts of5-(3',5'-dinitro-4-chlorobenzoylamino)-1-aminobenzene-Z-sulphonic acidin 1,000 parts of water having a temperature of 0 to 5 C., anddiazotization is eife'cted with 215 parts by volume of 4 N sodiumnitrite solution. The diazo suspension, which is acid to Congo paper, isadded to a suspension of 57.1 parts of 1-[4'-(a.-bromacrylamino)benzoylamino] 8 hydroxynaphthalene 3,6- disulphonic acid in 300 parts ofwater and 40 parts of sodium acetate. After coupling, the dyestuif iscompletely precipitated by the addition of sodium chloride, isolated byfiltration and then dried in vacuo at 60 to 70 C. The dyestulf soobtained dyes wool fast red shades.

Similar dyestuffs which also dye Wool fast red shades may be obtained byreplacing the 1-[4'-(ot-bromacrylamino) benzoylamino] 8hydroxynaphthalene 3,6- disulphonic acid with an equivalent proportionof one of the following coupling components.

1- [4'- a-bromacrylamino) -benzoylamino]-8-hydroxynaphthalene-4,6-disulphonic acid,

1- 3'- ot-bromacrylamino -benzoylamino]S-hydroxynaphthalene-4,6-disulphonic acid,

1- 3- a-bromacrylamino -benzoy1amin0]-8-hydroxynaphthalene-3,6-disulphonic acid and 1[4'-(3,5"-dinitro-4"-chlorobenzoylamino)benzoylamino]-8-hydroXynaphthalene-3,6- disulphonic acid.

Dyeing procedure 2 parts of the dyestuif obtained in the mannerdescribed in Example 1 are dissolved in 4,000 parts of water; 10 partsof sodium sulphate crystals are added and then 100 parts of well-wettedWool are entered into the dyebath so prepared at 40 to 50 C. 2 parts of40% acetic acid are then added, the dyebath is brought to the boilwithin half an hour, and dyeing is carried out at the boil for 45minutes. The wool is then rinsed in cold Water and dried. It is dyed ared shade which is fast to Washing and which possesses a good fastnessto light.

I claim:

1. Monoazo dyestuff which, in the form of the free acid, corresponds tothe formula SOsH in which one of the symbols Y represents a hydrogenatom and the other symbol Y represents a sulphonic acid group, Zrepresents alkyl or alkenyl containing up to 4 carbon atoms, phenyl,alkylcarboxamidophenyl, alkenylcarboxamidophenyl containing up to 4carbon atoms in said alkyl 2. A dyestuff as claimed in claim 1, whichcorresponds to the formula SIOaH Hois- SIOSH HO NHOOX2 where Xrepresents a lower alkyl or a lower alkoxy group, a phenyl or a group,one Y is hydrogen, the other Y is a sulfonic acid group, one Z ishydrogen and the other Z is a-bromoacrylamino.

4. The dyestuif according to claim 1, which corresponds to the formula803E OH NHCOCHs I NH 0 Q C: C H

Br S 0 H 5. The dyestuff according to claim 1, which corresponds to theformula OH NHCOG Br SOQH SOgH 6. The dyestufi according to claim 1,which corresponds to the formula NH 0 C=CH2 7. The dyestuif according toclaim 1, which corresponds to the formula S 0 11 OH ITIHC NHCO C=OH2 l S03H Br 8. The dyestuff according to claim 1, which corresponds to theformula S 0311 OH NH- I S 03H- 7 NH O O C C Hz 9. The dyestutf accordingto claim 1, which corresponds to the formula S aH OH NIHCO NHOO GCH2 1$03K Br NHCO CBr=CH2 SOaH ONHCO 0131:0112

10. The dyestuff according to claim 1, which corresponds to the formulaI on 171w OONHCO CHBrCHzBr S 03H NH0 0 CHCHzBr 11. The dyestuflfaccording to claim 1, which corresponds to the formula I onITIHCOO-NHCOCB1=CH2 12. The dyestuffs according to claim 1, whichcorrespond to the formula SOJH the symbols Y represents a hydrogen atomand the other symbol Y represents a sulfphonic acid group.

References Cited FOREIGN PATIENTS 10/1963 France 260'199 11/1966Switzerland 260199 CHARLES B. PARKER, Primary Examiner C. F. WARREN,Assistant Examiner US. Cl. X.R. 841, 50, 51

